CN105601031A - Treatment method of waste water produced during production of intermediate compound 4AA - Google Patents
Treatment method of waste water produced during production of intermediate compound 4AA Download PDFInfo
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- CN105601031A CN105601031A CN201510969180.9A CN201510969180A CN105601031A CN 105601031 A CN105601031 A CN 105601031A CN 201510969180 A CN201510969180 A CN 201510969180A CN 105601031 A CN105601031 A CN 105601031A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
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Abstract
The invention provides a treatment method of waste water produced during the production of intermediate compound 4AA. The method comprises the following steps: a, recycling a multifunctional solvent; b, recycling MVR salt; c, performing hydrogenation reduction modification treatment; d, performing two-phase anaerobic process; e, performing CASS process treatment; f, performing heterogeneous advanced oxidation; g, performing biological aeration filtration. The recycling of multifunctional solvent in the step a comprises recycling of methyl alcohol in waste water, recycling of chloroform, and recycling of ethyl acetate or normal hexane; the recycling of MVR salt in the step b indicates that waste water in the step a is fed to an evaporator for desalination through MVR evaporation treatment; hydrogenation reduction modification treatment in the step c indicates that the desalinated waste water is subjected to reduction modification; two-phase anaerobic process in the step d comprises normal temperature aerated stripping, and outlet water subjected to air stripping enters an anaerobic reactor; CASS process treatment in the step e indicates that waste water subjected to two-phase anaerobic process is fed to CASS process treatment; heterogeneous advanced oxidation in the step f comprises the step of feeding oxidizing agent to be subjected to aeration reaction with ferrite.
Description
Technical field
The present invention relates to a kind of processing method of pharmaceuticals industry waste water, relate in particular to a kind of processing for 4AA factory effluentMethod, belongs to field of waste water treatment.
Background technology
4-AA i.e. { 4-acetoxy-3-[1-(tertiary butyl dimethyl Si base) ethyl] aza cyclo-butanone } is to produce all carbonThe primary raw material of penems antibiotics bulk drug. 4AA, in reaction, extraction, salify, purge process, produces and contains greatlyThe high concentration hard-degraded organic waste water of amount pollutant, is characterized by: 1) high organic loading: COD up to 30000～200000mg/L, NH3-N content exceedes 600mg/L; 2) high saliferous: its content reaches 80～200g/L; 3) there is lifeThing inhibiting substances: residual organic solvent, surface reactive material etc.; 4) color heavy, smell weight. Visible, 4AA Industry WasteWater generates contaminant component is many, contaminant degradation is difficult, if unprocessed discharge will cause huge dirt to natureDye and and then destroy the natural ecological balance.
Domestic and international many scholars have carried out large quantity research aspect antibiotic waste water processing, and processing method mainly contains physical chemistry methodAnd bioanalysis. Wherein physical chemistry method mainly comprises coagulating sedimentation, absorption, air supporting and the method, particularly film place such as film separatesLogos exists that processing cost is high, complicated operation, easily cause secondary pollution problems. Bioanalysis is mainly to utilize microorganism to enterRow Anaerobic Treatment and Aerobic Process for Treatment, it has, and cost is low, recycling degree is high, but locating specific to antibiotic industrial wastewaterReason, due to antibiotic residue tire and organic solvent can severe inhibition anaerobe and the eubolism of aerobic microbiologicalActivity, is having a strong impact on the life-span of activated sludge and the treatment effect of industrial wastewater. If directly adopt Aerobic Process for Treatment, as profitDirectly process the waste water of this salt content up to 80～200g/L with aerobic activated sludge process, will be difficult to qualified discharge.
A kind of synthesis route of 4AA is taking L-threonine, stannous chloride, hydrochloric acid and natrium nitrosum as initiation material,Through diazo-reaction, annulation, substitution reaction, amidation process, rearrangement reaction, oxidation reaction and reduction reactionAfter obtain finished product.
Because 4AA synthesis route is long, intermediate product is many, the pollutant kind of generation is various, not yet have at present for4AA sewage that production process produces carries out the report of effectively processing.
Function of mechanical steam recompression technology (MechanicalVaporRecompression is called for short MVR), claims again heat pump techniques,Be the condensation latent heat of the indirect steam of re-using vaporized concentration process generation, to external world can thereby reduce evaporating concentration processA Technolqgy for Energy Economizing of source demand. The general principle of MVR technology is exactly the indirect steam that evaporator evaporation is produced,Through vapour compression machine mechanical compress, improve pressure and the saturation temperature of indirect steam, improve the indirect steam of heat contentSend vapo(u)rization system to, for supplementing or replacing fresh steam completely.
Summary of the invention
The object of the invention is for overcome the processing cost existing in existing antibiotic process for treating industrial waste water high, polluteThing is processed halfway deficiency, and the processing method of waste water in a kind of intermediate 4AA production is provided, and this waste water treatment process is outstandingIt is applicable to the processing of chemical synthesis bulk drug industrial wastewater, during especially for 4AA wastewater treatment, has processing costLow, the advantage such as high and process stabilizing of pollutants removal rate, the 4AA discharged wastewater met the national standard after this PROCESS FOR TREATMENT or enterStep is processed rear reuse.
Object of the present invention can be achieved through the following technical solutions:
During intermediate 4AA of the present invention produces, the processing method of waste water is that " multi-functional solvent recovering system+MVR salt reclaims+andes alsoFormer modification+diphasic anaerobic+cyclic activated sludge system+heterogeneous advanced oxidation+BAF " combination.
During intermediate 4AA of the present invention produces, the processing method of waste water is carried out as follows:
A. multi-functional solvent reclaims;
B.MVR salt reclaims;
C. hydrogenating reduction modification;
D. diphasic anaerobic;
E.CASS processes;
F. heterogeneous advanced oxidation;
G. BAF;
Multi-functional solvent described in a step reclaims and comprises that recovery, the recovery of chloroform, the ethyl acetate of methyl alcohol in waste water reclaimOr n-hexane reclaims;
Described in b step, the recovery of MVR salt is to send evaporimeter by the waste water of a step, through the desalination of MVR evaporation process;
Hydrogenating reduction modification described in C step is the wadding that the waste water after desalination adds 1 ‰-3 ‰ weight by b stepSolidifying agent sedimentation 1-1.5 hour; Then adjusting the pH value of waste water with pH value conditioning agent is 2-4, and blast aeration, maintains dissolvingOxygen 1-2mg/L carries out modified with reduction;
Diphasic anaerobic described in d step comprises: regulating the pH value of the water outlet of hydrogenating reduction modification is 9.5-10.5, normalTemperature aeration stripping 12-24 hour, wherein air water volume ratio 40-50: 1; Water outlet after stripping enters hydrolysis acidification pool processingAfter 8-12 hour, enter anaerobic reactor, time of staying 36-48 hour;
Cyclic activated sludge system processing described in e step is to send cyclic activated sludge system processing by d step through the waste water of diphasic anaerobic processing;
Heterogeneous advanced oxidation described in f step comprises: the pH value of adjusting water outlet is 3.0-3.5, in water outlet, adds oxygenAgent and ferrous salt aerated reaction 1.5-2 hour, adjusting pH value of waste water is 9-10 to Fe3+Precipitation completely;
In BAF described in g step, aeration time is 8-12 hour, and dissolved oxygen maintains 3-5mg/L, addsThe composite bacteria of nitrifier content more than 85%.
Object of the present invention can also be achieved through the following technical solutions:
Multi-functional solvent recycling of the present invention comprises the steps: that its function is mainly by multi-functional time in unitReceive Tower System and realize the recovery to Different solution in different waste water.
(1) recovery of methyl alcohol in methanol waste water: in waste water, methyl alcohol accounts for 60-70%, a small amount of ethyl acetate, benzinum. PurityRequire: methanol content 97%. Recovery tower uses TDV type high efficiency packing. Useless methyl alcohol is got to tower reactor through pump, opens steam and addsHeat, low-pressure steam conveying capacity 300kg/h opens each heat exchanger recirculated water simultaneously; Driving leading portion, overhead condenser condensate liquidInfinite reflux is to tower top, and after stable operation, tower top temperature progressively raises, and tower top temperature is stabilized in 64 DEG C. Closed to tower topLattice methyl alcohol, now partial reflux, part extraction, to pans, is up to the standards and puts into finished pot. The residual still that optionally discharges of stillResidual, tower reactor temperature reaches more than 102 DEG C, stops heating, obtains methyl alcohol, and waste water is discharged. Reclaiming methanol purity is 98%.
(2) containing the recovery of chloroform in chloroform waste water: in waste water, chloroform accounts for 86%, and other is ethyl acetate, water, Shao LiangshiOil ether. Purity requirement: chloroform > 97%.
Useless chloroform solution is got to tower reactor through pump, in the time that tower reactor has liquid level, opens Steam Heating, low-pressure steam 200kg/h, withTime open each heat exchanger cycling use of water, driving leading portion, the infinite reflux of overhead condenser condensate liquid is to tower top, after stable operation,Tower top temperature progressively raises, and tower top temperature is stabilized in 62 DEG C, and tower top can obtain qualified chloroform, now partial reflux, partExtraction, to pans, is up to the standards and puts into finished pot. The residual optionally discharge of still, puts still when residual, and tower reactor temperature reaches 102 DEG CAbove, stop heating, in tower substantially without chloroform. Reclaiming chloroform purity is 98%.
(3) ethyl acetate reclaims: reclaim liquid composition: ethyl acetate accounts for 92% (water: ethyl ester=1:13), and other isDMF, chloroform, water. Purity requirement: ethyl acetate content > 97%.
When tower reactor temperature stabilization is during at 61 DEG C, chloroform first steams from tower top. Because ethyl acetate and water are depressed at normal atmosphereAzeotropic point is 70.4 DEG C, and in the time that temperature reaches approximately 70 DEG C, the two is simultaneously from tower top output, consist of 94% ethyl acetate and6% water, enters through this mixture after the assay was approved the drain sump that band stirs, and inside has water absorbing agent (with anhydrous sodium sulfate), normal temperatureRemove most water, obtain the ethyl acetate of purity approximately 98%, then remove solid impurity with filter.
Flocculant described in C step be bodied ferric sulfate, aluminium polychloride one of them or both mix with any proportioning mixedClose liquid.
The combination that hydrogenating reduction modification catalyst used described in C step is Fe/C/Cu, its mass ratio is Fe:Cu：C＝70-80:10:1。
PH adjusting agent described in C step is inorganic acid.
Described pH adjusting agent is the mixed liquor that sulfuric acid, hydrochloric acid one of them or both mix with any proportioning.
(4) n-hexane reclaims: reclaim liquid composition: n-hexane accounts for 80%, and other is benzinum. Purity requirement > 85%.First remove lighter benzinum (pentane), afterwards, total reflux operation, in the time that tower top temperature is stabilized in 69 DEG C, collection unitPoint n-hexane is to pans, enters finished pot after qualified after measured. Column bottom temperature reaches 90 DEG C of explanation raffinates and is not substantially just containingHexane, the waste liquid of can draining.
In described MVR salt recycling unit, comprise the steps: to select MVR falling film evaporator to substitute traditional threeSingle-effect evaporator. The downward concurrent flow of liquid and steam. Feed liquid is preheated to boiling temperature through preheater, divides through the liquid at topCloth apparatus forms uniform liquid film and enters heating tube, and part evaporation in pipe. Indirect steam and concentrate also flow in pipeAnd under. the time of staying of feed liquid in evaporimeter is short, can adapt to the evaporation of thermosensitive solution. After MVR evaporation process,Desalting efficiency reaches 99%.
Described modified with reduction unit comprises the steps: that the waste water after desalination adds 1 ‰-3 ‰ flocculant sedimentation1-1.5 hour; The pH value that uses pH adjusting agent to adjust waste water is 3.0 left and right, and blast aeration maintains dissolved oxygen 1-2mg/LCarry out modified with reduction. Wherein said pH adjusting agent can, for conventional inorganic acid, be preferably sulfuric acid, hydrochloric acid or both groupsClose; Described flocculant is conventional flocculant for treating waste water, is preferably bodied ferric sulfate, aluminium polychloride or bothCombination. The essence of this processing unit is, by hydrogenation reduction by the heterocycle of difficult for biological degradation, stable chemical nature,The macromolecular structures of many rings are changed, and are some or all ofly converted into biodegradable material, are follow-up biology placeReason unit provides good treatment conditions. The combination that wherein said hydrogenation reduction catalyst used is Fe/C/Cu,Its mass ratio is Fe:Cu:C=70-80:10:1; In reactor, add specialty metal Pt, the Pd of mass content 1 ‰ amountsOr both mixtures are for strengthening reduction and the organic removal ability of Fe, after modified with reduction processing unit4AA waste water COD clearance reaches 20%-30%.
Described diphasic anaerobic unit comprises: regulating the pH of the water outlet of modified with reduction cell processing is 9.5-10.5, and normal temperature exposes to the sunAir-blowing takes off 12-24 hour, wherein air water volume ratio 40-50: 1; Water outlet after stripping enters hydrolysis acidification pool and processes 8-12After hour, enter anaerobic reactor, anaerobic reactor is selected EGSB tank, time of staying 36-48 hour. In waste water, ammonia nitrogen containsMeasured the growth metabolism that high energy suppresses anaerobe, the ammonia-nitrogen content of modified with reduction water outlet after treatment after stripping is reduced toThe tolerance range (< 300mg/L) of anaerobe, can reach through the COD clearance of the waste water of diphasic anaerobic step process60％-70％。
In described CASS processing unit, the dissolved oxygen of waste water maintains 3-5mg/L, through the ammonia of the waste water of cyclic activated sludge system processingNitrogen removal efficiency is 97-99%, and nitrogen removal rate is 70-80%, and the clearance of COD is 85-90%.
Described advanced oxidation unit comprises: the pH value of adjusting water outlet is 3.0-3.5, in water outlet, adds oxidant and AsiaMolysite aerated reaction 1.5-2 hour, adjusting wastewater pH is 9-10 to Fe3+Precipitation completely. Wherein said oxidant is peroxideChange hydrogen, clorox, ferrate or its combination, preferably 30% hydrogenperoxide steam generator, its addition is 1-3ml/L;Described ferrous salt is ferrous sulfate, frerrous chloride or its combination, and its addition is 0.5-1.5g/L. Waste water is by senior oxygenChange step and can effectively remove colourity in waste water and the mesostate of hardly degraded organic substance and generation, finish dealing withRear water outlet COD is less than 100mg/L.
In described BAF unit, aeration time is 8-12 hour, and dissolved oxygen maintains 3-5mg/L, adds nitratedThe composite bacteria of bacterial content more than 85%. COD through the water outlet of BAF processing is less than 50mg/L.
Oxidant described in f step be hydrogen peroxide, clorox, perferrite, ferrate one of them or two kinds orThe two or more mixed liquors that mix with any proportioning.
Described oxidant is 30% hydrogenperoxide steam generator, and its addition is 1-3ml/L; Described ferrous salt is sulfuric acid AsiaThe mixed liquor that iron, frerrous chloride one of them or both mix with any proportioning, its addition is 0.5-1.5g/L.
The present invention has following beneficial effect:
The each treatment combination of the present invention is reasonable, and treatment effeciency is high, technology stability good, has embodied 4AA wastewater treatment is imitatedThe associated treatment effect of fruit.
(1) recovery to methyl alcohol, chloroform, ethyl acetate, n-hexane by multi-functional recovery tower, is removing high concentration dirtWhen dying thing, reclaim the solvent that has recycling to be worth, saved production cost.
(2) by selecting MVR falling film evaporator to reclaim salt, make salt rejection rate reach 99%, substantially eliminate high salinityTo the inhibition of subsequent treatment process. By reducing the use amount of fresh steam, reduce the consumption of producing power cost, saveProduction cost.
(3) comprehensive 4AA waste water carried out modified with reduction processing and adopts diphasic anaerobic technique, making residual molten on a small quantityMatchmaker's concentration significantly reduces. Utilize hydrolysis acidification to react the good removal effect to sulfate radical, in elimination water, sulfate radical is to anaerobismProduce the inhibitory action of methane phase, improve treatment effect and stability.
(4) by cyclic activated sludge system, the organic matter in waste water and ammonia nitrogen are further degraded, improve biological treatment outlet effect,Because it does not need a large amount of sludge refluxes, automaticity is high, so construction and operating cost are low.
(5) adopt advanced oxidation processes, improve hardly degraded organic substance and colourity by suitable supplemental oxidant and precipitating reagentRemoval, thereby guarantee the qualified discharge of water outlet, also can meet the upgrading requirement of sewage treatment process in the future.
(6) by adding high-performance bio degraded composite bacteria, the organic matter in waste water and ammonia nitrogen are further degraded, fullThe low ammonia nitrogen index that has ensured water outlet when foot COD draining qualified discharge, does not need a large amount of sludge refluxes in this unit,Automaticity is high, so equipment construction expense and operating cost are low, and the processing reason of more composite safe environmental protection, high-efficiency low-carbonRead.
Brief description of the drawings
Fig. 1 is the process chart of the embodiment of the present invention.
Detailed description of the invention
Below by specific embodiment, and the present invention is further described in conjunction with processing technological flow figure of the present invention, this areaTechnical staff should be able to know, and the present invention is not only limited to this embodiment.
Embodiment 1:
Method of the present invention is carried out as follows:
A. multi-functional solvent reclaims;
B.MVR salt reclaims;
C. hydrogenating reduction modification;
D. diphasic anaerobic;
E.CASS processes;
F. heterogeneous advanced oxidation;
G. BAF;
(1) recovery of methyl alcohol in methanol waste water: in waste water, methyl alcohol accounts for 60%, a small amount of ethyl acetate, benzinum. Purity requirement:Methanol content > 97%. Recovery tower uses TDV type high efficiency packing. Useless methyl alcohol is got to tower reactor through pump, opens Steam Heating, lowPress steam conveying capacity 300kg/h, open each heat exchanger recirculated water simultaneously; Driving leading portion, the infinite reflux of overhead condenser condensate liquidTo tower top, after stable operation, tower top temperature progressively raises, and tower top temperature is stabilized in 64 DEG C. Obtain qualified methyl alcohol to tower top,Now partial reflux, part extraction, to pans, is up to the standards and puts into finished pot. Still is residual, and optionally to discharge still residual, tower reactorTemperature reaches more than 102 DEG C, stops heating, obtains methyl alcohol, and waste water is discharged. Reclaiming methanol purity is 98%.
(2) containing the recovery of chloroform in chloroform waste water: in waste water, chloroform accounts for 86%, and other is ethyl acetate, water, Shao LiangshiOil ether. Purity requirement: chloroform > 97%.
Useless chloroform solution is got to tower reactor through pump, in the time that tower reactor has liquid level, opens Steam Heating, low-pressure steam 200kg/h, withTime open each heat exchanger cycling use of water, driving leading portion, the infinite reflux of overhead condenser condensate liquid is to tower top, after stable operation,Tower top temperature progressively raises, and tower top temperature is stabilized in 62 DEG C, and tower top can obtain qualified chloroform, now partial reflux, partExtraction, to pans, is up to the standards and puts into finished pot. The residual optionally discharge of still, puts still when residual, and tower reactor temperature reaches 102 DEG CAbove, stop heating, in tower substantially without chloroform. Reclaiming chloroform purity is 98%.
(3) ethyl acetate reclaims: reclaim liquid composition: ethyl acetate accounts for 92% (water: ethyl ester=1:13 weight part ratio),Other is DMF, chloroform, water. Purity requirement: ethyl acetate content > 97%.
When tower reactor temperature stabilization is during at 61 DEG C, chloroform first steams from tower top. Because ethyl acetate and water are depressed at normal atmosphereAzeotropic point is 70.4 DEG C, and in the time that temperature reaches approximately 70 DEG C, the two is simultaneously from tower top output, consist of 94% ethyl acetate and6% water, enters through this mixture after the assay was approved the drain sump that band stirs, and inside has water absorbing agent (with anhydrous sodium sulfate), normal temperatureRemove most water, obtain the ethyl acetate of purity approximately 98%, then remove solid impurity with filter.
Flocculant described in C step be bodied ferric sulfate, aluminium polychloride one of them or both mix with any proportioning mixedClose liquid.
The combination that hydrogenating reduction modification catalyst used described in C step is Fe/C/Cu, its mass ratio is Fe:Cu：C＝70-80:10:1。
PH adjusting agent described in C step is inorganic acid.
Described pH adjusting agent is the mixed liquor that sulfuric acid, hydrochloric acid one of them or both mix with any proportioning.
(4) n-hexane reclaims: reclaim liquid composition: n-hexane accounts for 80%, and other is benzinum. Purity requirement > 85%.First remove lighter benzinum (pentane), afterwards, total reflux operation, in the time that tower top temperature is stabilized in 69 DEG C, collection unitPoint n-hexane is to pans, enters finished pot after qualified after measured. Column bottom temperature reaches 90 DEG C of explanation raffinates and is not substantially just containingHexane, the waste liquid of can draining.
In described MVR salt recycling unit, comprise the steps: to select MVR falling film evaporator to substitute traditional threeSingle-effect evaporator. The downward concurrent flow of liquid and steam. Feed liquid is preheated to boiling temperature through preheater, divides through the liquid at topCloth apparatus forms uniform liquid film and enters heating tube, and part evaporation in pipe. Indirect steam and concentrate also flow in pipeAnd under. the time of staying of feed liquid in evaporimeter is short, can adapt to the evaporation of thermosensitive solution. After MVR evaporation process,Desalting efficiency reaches 99%.
Described modified with reduction unit comprises the steps: that the waste water after desalination adds 3 ‰ flocculant sedimentation 1 hour;Using pH adjusting agent to adjust the pH value of waste water is 3.0 left and right, and blast aeration maintains dissolved oxygen 2mg/L and reduces and changeProperty. Wherein said pH adjusting agent can, for conventional inorganic acid, be preferably sulfuric acid, hydrochloric acid or both combinations; Described waddingSolidifying agent is conventional flocculant for treating waste water, is preferably bodied ferric sulfate, aluminium polychloride or both combinations. This placeThe essence of reason unit is by hydrogenation reduction, the large of the heterocycle of difficult for biological degradation, stable chemical nature, many rings to be dividedMinor structure is changed, and is some or all ofly converted into biodegradable material, for follow-up biological processing unit providesGood treatment conditions. The combination that wherein said hydrogenation reduction catalyst used is Fe/C/Cu, its mass ratioFor Fe:Cu:C=70-80:10:1; In reactor, add specialty metal Pt, the Pd of mass content 1 ‰ amounts or bothMixture for strengthening reduction and the organic removal ability of Fe, 4AA waste water after modified with reduction processing unitCOD clearance reaches 20%.
Described diphasic anaerobic unit comprises: regulating the pH of the water outlet of modified with reduction cell processing is 9.5, and normal temperature aeration blowsDe-24 hours, wherein air water volume ratio 40: 1; Water outlet after stripping enters hydrolysis acidification pool processing and enters and detest after 12 hoursOxygen reactor, anaerobic reactor is selected EGSB tank, 36 hours time of staying. In waste water, ammonia-nitrogen content is crossed high energy inhibition anaerobismMicrobial growth metabolism, the ammonia-nitrogen content of modified with reduction water outlet after treatment after stripping is reduced to the tolerance of anaerobeScope (< 300mg/L), can reach 70% through the COD clearance of the waste water of diphasic anaerobic step process.
In described CASS processing unit, the dissolved oxygen of waste water maintains 3mg/L, through the ammonia nitrogen of the waste water of cyclic activated sludge system processingClearance is 99%, and the clearance that nitrogen removal rate is 70%, COD is 90%.
Described advanced oxidation unit comprises: the pH value of adjusting water outlet is 3.0, in water outlet, adds oxidant and ferrous saltAerated reaction 2 hours, regulating wastewater pH is 9 to Fe3+Precipitation completely. Wherein said oxidant is hydrogen peroxide, inferior chlorineAcid sodium, ferrate or its combination, preferably 30% hydrogenperoxide steam generator, its addition is 3ml/L; Described ferrous saltFor ferrous sulfate, frerrous chloride or its combination, its addition is 0.5g/L. Waste water can be effective by advanced oxidation stepColourity in removal waste water and the mesostate of hardly degraded organic substance and generation, after finishing dealing with, water outlet COD is less than100mg/L。
In described BAF unit, aeration time is 12 hours, and dissolved oxygen maintains 3mg/L, adds nitrifier and containsThe composite bacteria of amount more than 85%. COD through the water outlet of BAF processing is less than 50mg/L.
Oxidant described in f step be hydrogen peroxide, clorox, perferrite, ferrate one of them or two kinds orThe two or more mixed liquors that mix with any proportioning.
Described oxidant is 30% hydrogenperoxide steam generator, and its addition is 3ml/L; Described ferrous salt be ferrous sulfate,The mixed liquor that frerrous chloride one of them or both mix with any proportioning, its addition is 0.5g/L.
Embodiment 2:
Method of the present invention is carried out as follows:
A. multi-functional solvent reclaims;
B.MVR salt reclaims;
C. hydrogenating reduction modification;
D. diphasic anaerobic;
E.CASS processes;
F. heterogeneous advanced oxidation;
G. BAF;
(1) recovery of methyl alcohol in methanol waste water: in waste water, methyl alcohol accounts for 70%, a small amount of ethyl acetate, benzinum. Purity requirement:Methanol content > 97%. Recovery tower uses TDV type high efficiency packing. Useless methyl alcohol is got to tower reactor through pump, opens Steam Heating, lowPress steam conveying capacity 300kg/h, open each heat exchanger recirculated water simultaneously; Driving leading portion, the infinite reflux of overhead condenser condensate liquidTo tower top, after stable operation, tower top temperature progressively raises, and tower top temperature is stabilized in 64 DEG C. Obtain qualified methyl alcohol to tower top,Now partial reflux, part extraction, to pans, is up to the standards and puts into finished pot. Still is residual, and optionally to discharge still residual, tower reactorTemperature reaches more than 102 DEG C, stops heating, obtains methyl alcohol, and waste water is discharged. Reclaiming methanol purity is 98%.
(2) containing the recovery of chloroform in chloroform waste water: in waste water, chloroform accounts for 86%, and other is ethyl acetate, water, Shao LiangshiOil ether. Purity requirement: chloroform > 97%.
Useless chloroform solution is got to tower reactor through pump, in the time that tower reactor has liquid level, opens Steam Heating, low-pressure steam 200kg/h, withTime open each heat exchanger cycling use of water, driving leading portion, the infinite reflux of overhead condenser condensate liquid is to tower top, after stable operation,Tower top temperature progressively raises, and tower top temperature is stabilized in 62 DEG C, and tower top can obtain qualified chloroform, now partial reflux, partExtraction, to pans, is up to the standards and puts into finished pot. The residual optionally discharge of still, puts still when residual, and tower reactor temperature reaches 102 DEG CAbove, stop heating, in tower substantially without chloroform. Reclaiming chloroform purity is 98%.
(3) ethyl acetate reclaims: reclaim liquid composition: ethyl acetate accounts for 92% (water: ethyl ester=1:13 weight portion),Other is DMF, chloroform, water. Purity requirement: ethyl acetate content > 97%.
When tower reactor temperature stabilization is during at 61 DEG C, chloroform first steams from tower top. Because ethyl acetate and water are depressed at normal atmosphereAzeotropic point is 70.4 DEG C, and in the time that temperature reaches approximately 70 DEG C, the two is simultaneously from tower top output, consist of 94% ethyl acetate and6% water, enters through this mixture after the assay was approved the drain sump that band stirs, and inside has water absorbing agent (with anhydrous sodium sulfate), normal temperatureRemove most water, obtain the ethyl acetate of purity approximately 98%, then remove solid impurity with filter.
Flocculant described in C step be bodied ferric sulfate, aluminium polychloride one of them or both mix with any proportioning mixedClose liquid.
The combination that hydrogenating reduction modification catalyst used described in C step is Fe/C/Cu, its mass ratio is Fe:Cu：C＝70-80:10:1。
PH adjusting agent described in C step is inorganic acid.
Described pH adjusting agent is the mixed liquor that sulfuric acid, hydrochloric acid one of them or both mix with any proportioning.
(4) n-hexane reclaims: reclaim liquid composition: n-hexane accounts for 80%, and other is benzinum. Purity requirement > 85%.First remove lighter benzinum (pentane), afterwards, total reflux operation, in the time that tower top temperature is stabilized in 69 DEG C, collection unitPoint n-hexane is to pans, enters finished pot after qualified after measured. Column bottom temperature reaches 90 DEG C of explanation raffinates and is not substantially just containingHexane, the waste liquid of can draining.
In described MVR salt recycling unit, comprise the steps: to select MVR falling film evaporator to substitute traditional threeSingle-effect evaporator. The downward concurrent flow of liquid and steam. Feed liquid is preheated to boiling temperature through preheater, divides through the liquid at topCloth apparatus forms uniform liquid film and enters heating tube, and part evaporation in pipe. Indirect steam and concentrate also flow in pipeAnd under. the time of staying of feed liquid in evaporimeter is short, can adapt to the evaporation of thermosensitive solution. After MVR evaporation process,Desalting efficiency reaches 99%.
Described modified with reduction unit comprises the steps: that the waste water after desalination adds 1 ‰ flocculant sedimentation 1.5 littleTime; Using pH adjusting agent to adjust the pH value of waste water is 3.0 left and right, and blast aeration maintains dissolved oxygen 1mg/L and goes backFormer modification. Wherein said pH adjusting agent can, for conventional inorganic acid, be preferably sulfuric acid, hydrochloric acid or both combinations; InstituteStating flocculant is conventional flocculant for treating waste water, is preferably bodied ferric sulfate, aluminium polychloride or both combinations.The essence of this processing unit is, by hydrogenation reduction by the heterocycle of difficult for biological degradation, stable chemical nature, many ringsMacromolecular structure is changed, and is some or all ofly converted into biodegradable material, is follow-up biological processing unitGood treatment conditions are provided. The combination that wherein said hydrogenation reduction catalyst used is Fe/C/Cu, its matterAmount is than being Fe:Cu:C=70-80:10:1; In reactor, add mass content 1 ‰ amounts specialty metal Pt, Pd orBoth mixtures are for strengthening reduction and the organic removal ability of Fe, 4AA after modified with reduction processing unitWaste water COD clearance reaches 30%.
Described diphasic anaerobic unit comprises: regulating the pH of the water outlet of modified with reduction cell processing is 10.5, and normal temperature aeration blowsDe-12 hours, wherein air water volume ratio 50: 1; Water outlet after stripping enters hydrolysis acidification pool processing and enters and detest after 8 hoursOxygen reactor, anaerobic reactor is selected EGSB tank, 48 hours time of staying. In waste water ammonia-nitrogen content cross high energy suppress detestThe growth metabolism of oxygen animalcule, the ammonia-nitrogen content of modified with reduction water outlet after treatment after stripping is reduced to the resistance to of anaerobeBe subject to scope (< 300mg/L), can reach 60% through the COD clearance of the waste water of diphasic anaerobic step process.
In described CASS processing unit, the dissolved oxygen of waste water maintains 5mg/L, through the ammonia nitrogen of the waste water of cyclic activated sludge system processingClearance is 97%, and the clearance that nitrogen removal rate is 80%, COD is 85%.
Described advanced oxidation unit comprises: the pH value of adjusting water outlet is 3.5, in water outlet, adds oxidant and ferrous saltAerated reaction 1.5 hours, regulating wastewater pH is 10 to Fe3+Precipitation completely. Wherein said oxidant is hydrogen peroxide, inferiorSodium chlorate, ferrate or its combination, preferably 30% hydrogenperoxide steam generator, its addition is 1ml/L; Described ferrous ironSalt is ferrous sulfate, frerrous chloride or its combination, and its addition is 1.5g/L. Waste water can have by advanced oxidation stepColourity in effect removal waste water and the mesostate of hardly degraded organic substance and generation, after finishing dealing with, water outlet COD is littleIn 100mg/L.
In described BAF unit, aeration time is 8 hours, and dissolved oxygen maintains 5mg/L, adds nitrifier contentComposite bacteria more than 85%. COD through the water outlet of BAF processing is less than 50mg/L.
Oxidant described in f step be hydrogen peroxide, clorox, perferrite, ferrate one of them or two kinds orThe two or more mixed liquors that mix with any proportioning.
Described oxidant is 30% hydrogenperoxide steam generator, and its addition is 1ml/L; Described ferrous salt be ferrous sulfate,The mixed liquor that frerrous chloride one of them or both mix with any proportioning, its addition is 1.5g/L.
Embodiment 3:
Method of the present invention is carried out as follows:
A. multi-functional solvent reclaims;
B.MVR salt reclaims;
C. hydrogenating reduction modification;
D. diphasic anaerobic;
E.CASS processes;
F. heterogeneous advanced oxidation;
G. BAF;
(1) recovery of methyl alcohol in methanol waste water: in waste water, methyl alcohol accounts for 65%, a small amount of ethyl acetate, benzinum. Purity requirement:Methanol content > 97%. Recovery tower uses TDV type high efficiency packing. Useless methyl alcohol is got to tower reactor through pump, opens Steam Heating, lowPress steam conveying capacity 300kg/h, open each heat exchanger recirculated water simultaneously; Driving leading portion, the infinite reflux of overhead condenser condensate liquidTo tower top, after stable operation, tower top temperature progressively raises, and tower top temperature is stabilized in 64 DEG C. Obtain qualified methyl alcohol to tower top,Now partial reflux, part extraction, to pans, is up to the standards and puts into finished pot. Still is residual, and optionally to discharge still residual, tower reactorTemperature reaches more than 102 DEG C, stops heating, obtains methyl alcohol, and waste water is discharged. Reclaiming methanol purity is 98%.
(2) containing the recovery of chloroform in chloroform waste water: in waste water, chloroform accounts for 86%, and other is ethyl acetate, water, Shao LiangshiOil ether. Purity requirement: chloroform > 97%.
Useless chloroform solution is got to tower reactor through pump, in the time that tower reactor has liquid level, opens Steam Heating, low-pressure steam 200kg/h, withTime open each heat exchanger cycling use of water, driving leading portion, the infinite reflux of overhead condenser condensate liquid is to tower top, after stable operation,Tower top temperature progressively raises, and tower top temperature is stabilized in 62 DEG C, and tower top can obtain qualified chloroform, now partial reflux, partExtraction, to pans, is up to the standards and puts into finished pot. The residual optionally discharge of still, puts still when residual, and tower reactor temperature reaches 102 DEG CAbove, stop heating, in tower substantially without chloroform. Reclaiming chloroform purity is 98%.
(3) ethyl acetate reclaims: reclaim liquid composition: ethyl acetate accounts for 92% (water: ethyl ester=1:13 patent part),Other is DMF, chloroform, water. Purity requirement: ethyl acetate content > 97%.
When tower reactor temperature stabilization is during at 61 DEG C, chloroform first steams from tower top. Because ethyl acetate and water are depressed at normal atmosphereAzeotropic point is 70.4 DEG C, and in the time that temperature reaches approximately 70 DEG C, the two is simultaneously from tower top output, consist of 94% ethyl acetate and6% water, enters through this mixture after the assay was approved the drain sump that band stirs, and inside has water absorbing agent (with anhydrous sodium sulfate), normal temperatureRemove most water, obtain the ethyl acetate of purity approximately 98%, then remove solid impurity with filter.
Flocculant described in C step be bodied ferric sulfate, aluminium polychloride one of them or both mix with any proportioning mixedClose liquid.
The combination that hydrogenating reduction modification catalyst used described in C step is Fe/C/Cu, its mass ratio is Fe:Cu：C＝70-80:10:1。
PH adjusting agent described in C step is inorganic acid.
Described pH adjusting agent is the mixed liquor that sulfuric acid, hydrochloric acid one of them or both mix with any proportioning.
(4) n-hexane reclaims: reclaim liquid composition: n-hexane accounts for 80%, and other is benzinum. Purity requirement > 85%.First remove lighter benzinum (pentane), afterwards, total reflux operation, in the time that tower top temperature is stabilized in 69 DEG C, collection unitPoint n-hexane is to pans, enters finished pot after qualified after measured. Column bottom temperature reaches 90 DEG C of explanation raffinates and is not substantially just containingHexane, the waste liquid of can draining.
In described MVR salt recycling unit, comprise the steps: to select MVR falling film evaporator to substitute traditional threeSingle-effect evaporator. The downward concurrent flow of liquid and steam. Feed liquid is preheated to boiling temperature through preheater, divides through the liquid at topCloth apparatus forms uniform liquid film and enters heating tube, and part evaporation in pipe. Indirect steam and concentrate also flow in pipeAnd under. the time of staying of feed liquid in evaporimeter is short, can adapt to the evaporation of thermosensitive solution. After MVR evaporation process,Desalting efficiency reaches 99%.
Described modified with reduction unit comprises the steps: that the waste water after desalination adds 2 ‰ flocculant sedimentation 1.2 littleTime; Using pH adjusting agent to adjust the pH value of waste water is 3.0 left and right, and blast aeration maintains dissolved oxygen 1.5mg/L and carries outModified with reduction. Wherein said pH adjusting agent can, for conventional inorganic acid, be preferably sulfuric acid, hydrochloric acid or both combinations;Described flocculant is conventional flocculant for treating waste water, is preferably bodied ferric sulfate, aluminium polychloride or both combinations.The essence of this processing unit is, by hydrogenation reduction by the heterocycle of difficult for biological degradation, stable chemical nature, many ringsMacromolecular structure is changed, and is some or all ofly converted into biodegradable material, is follow-up biological processing unitGood treatment conditions are provided. The combination that wherein said hydrogenation reduction catalyst used is Fe/C/Cu, its matterAmount is than being Fe:Cu:C=70-80:10:1; In reactor, add mass content 1 ‰ amounts specialty metal Pt, Pd orBoth mixtures are for strengthening reduction and the organic removal ability of Fe, 4AA after modified with reduction processing unitWaste water COD clearance reaches 25%.
Described diphasic anaerobic unit comprises: regulating the pH of the water outlet of modified with reduction cell processing is 10.0, and normal temperature aeration blowsDe-18 hours, wherein air water volume ratio 45: 1; Water outlet after stripping enters hydrolysis acidification pool processing and enters and detest after 10 hoursOxygen reactor, anaerobic reactor is selected EGSB tank, 42 hours time of staying. In waste water, ammonia-nitrogen content is crossed high energy inhibition anaerobismMicrobial growth metabolism, the ammonia-nitrogen content of modified with reduction water outlet after treatment after stripping is reduced to the tolerance of anaerobeScope (< 300mg/L), can reach 65% through the COD clearance of the waste water of diphasic anaerobic step process.
In described CASS processing unit, the dissolved oxygen of waste water maintains 4mg/L, through the ammonia nitrogen of the waste water of cyclic activated sludge system processingClearance is 98%, and the clearance that nitrogen removal rate is 75%, COD is 87%.
Described advanced oxidation unit comprises: the pH value of adjusting water outlet is 3.2, in water outlet, adds oxidant and ferrous saltAerated reaction 1.8 hours, regulating wastewater pH is 9.5 to Fe3+Precipitation completely. Wherein said oxidant be hydrogen peroxide,Clorox, ferrate or its combination, preferably 30% hydrogenperoxide steam generator, its addition is 2ml/L; Described AsiaMolysite is ferrous sulfate, frerrous chloride or its combination, and its addition is 1.0g/L. Waste water can by advanced oxidation stepThe effectively colourity in removal waste water and the mesostate of hardly degraded organic substance and generation, water outlet COD after finishing dealing withBe less than 100mg/L.
In described BAF unit, aeration time is 10 hours, and dissolved oxygen maintains 4mg/L, adds nitrifier and containsThe composite bacteria of amount more than 85%. COD through the water outlet of BAF processing is less than 50mg/L.
Oxidant described in f step be hydrogen peroxide, clorox, perferrite, ferrate one of them or two kinds orThe two or more mixed liquors that mix with any proportioning.
Described oxidant is 30% hydrogenperoxide steam generator, and its addition is 2ml/L; Described ferrous salt be ferrous sulfate,The mixed liquor that frerrous chloride one of them or both mix with any proportioning, its addition is 1.0g/L.
Embodiment 4:
Certain pharmacy group company year is produced 15 tons of 4AA products, and the sewage total amount that produce every day is about 300 cubes. Production workSkill is taking L-threonine, stannous chloride, hydrochloric acid and natrium nitrosum as initiation material, through diazo-reaction, annulation,After substitution reaction, amidation process, rearrangement reaction, oxidation reaction and reduction reaction, obtain finished product
Factory effluent is through entering comprehensive adjustment pond after row outside workshop, and mixed COD, NH3-N, total salt are respectively60000mg/L, 700mg/L, 180000mg/L. Containing solvent waste water, after recovery tower, COD reduces to 6000mg/L. Waste waterAfter MVR evaporimeter, COD, NH3-N, total salt are respectively 7000mg/L, 400mg/L, 1700mg/L. After desalinationWaste water adds 1 ‰-3 ‰ flocculant sedimentation 1-1.5 hour; The pH value that uses sulfuric acid to adjust waste water is 3.0 left and right, andBlast aeration maintains dissolved oxygen 1-2mg/L and carries out modified with reduction, and through the clearance of this processing unit COD, 25%, institute producesRaw mud is drained in sedimentation basin 1.
In the diphasic anaerobic stage, waste water normal temperature aeration stripping enters hydrolysis acidification pool after (steam-water ratio 45: 1) in 14 hours,In hydrolysis acidification pool, process and within 12 hours, enter EGSB anaerobic reaction-pot through hydrolysis acidification flora, through comprising that methanogen existsInterior anaerobic bacteria flora is processed after 48 hours and is entered CASS processing unit. The COD clearance in this stage reaches 60-70%,COD, the NH3-N of anaerobic effluent are down to respectively 2000mg/L, 200mg/L. The anaerobic sludge producing except reflux, itsMore than drain into sedimentation basin 2, finally enter sludge treating system.
At CASS processing unit, keeping the dissolved oxygen of waste water is 3-5mg/L, and waste water stops 24 and enters advanced oxidation after littleUnit. The ammonia nitrogen removal frank in this stage is that the clearance of 96%, COD is 90%, and COD, the NH3-N of outputted aerobic water divideWei 200mg/L, 8mg/L, the excess sludge producing therebetween enters sludge treating system through sedimentation basin 3.
Outputted aerobic water enters behind advanced oxidation unit, regulates pH value to 3.5, adds hydrogen peroxide with the ratio of 1.5ml/LSolution, adds ferrous sulfate with the ratio of 0.5g/L, aerated reaction 1.5 hours; Water outlet is by adding NaOH adjust pHTo 9, add 1 ‰ flocculation aid polyacrylamide, form ferric iron Fe (OH)3Precipitation, discharges water outlet COD through sedimentation basin 3For 80mg/L. Water outlet COD, NH3-N after BAF is processed 10 hours are respectively 45mg/L, 1mg/L row up to standardPut.
Claims (8)
- Intermediate 4AA produce in the processing method of waste water, it is characterized in that the method carries out as follows:A. multi-functional solvent reclaims;B.MVR salt reclaims;C. hydrogenating reduction modification;D. diphasic anaerobic;E.CASS processes;F. heterogeneous advanced oxidation;G. BAF;Multi-functional solvent described in a step reclaims the recovery, the recovery of chloroform, the ethyl acetate recovery or just own that comprise methyl alcohol in waste waterAlkane reclaims;Described in b step, the recovery of MVR salt is to send evaporimeter by the waste water of a step, through the desalination of MVR evaporation process;Hydrogenating reduction modification described in C step is that the waste water after desalination adds the flocculant of 1 ‰-3 ‰ weight heavy by b step1-1.5 hour falls; Then adjusting the pH value of waste water with pH value conditioning agent is 2-4, and blast aeration, maintains dissolved oxygen 1-2mg/LCarry out modified with reduction;Diphasic anaerobic described in d step comprises: regulating the pH value of the water outlet of hydrogenating reduction modification is 9.5-10.5, and normal temperature exposes to the sunAir-blowing takes off 12-24 hour, wherein air water volume ratio 40-50: 1; Water outlet after stripping enters hydrolysis acidification pool and processes 8-12After hour, enter anaerobic reactor, time of staying 36-48 hour;Cyclic activated sludge system processing described in e step is to send cyclic activated sludge system processing by d step through the waste water of diphasic anaerobic processing;Heterogeneous advanced oxidation described in f step comprises: the pH value of adjusting water outlet is 3.0-3.5, in water outlet, addsOxidant and ferrous salt aerated reaction 1.5-2 hour, adjusting pH value of waste water is 9-10 to Fe3+Precipitation completely;In BAF described in g step, aeration time is 8-12 hour, and dissolved oxygen maintains 3-5mg/L, adds nitratedThe composite bacteria of bacterial content more than 85%.
- 2. the processing method of waste water in a kind of intermediate 4AA production according to claim 1, is characterized in that a step instituteThe recovery of the methyl alcohol of stating is that waste water is entered by recovery tower top, and upper temp is controlled at 64 DEG C, when heating up in recovery tower bottomTo 102 DEG C of >, stop heating, obtain methyl alcohol, waste water is discharged;The recovery of described chloroform is that waste water is entered by recovery tower top, and upper temp is controlled at 61 DEG C, when heating up in recovery tower bottomTo 102 DEG C of >, stop heating, obtain chloroform, waste water is discharged;The recovery of described ethyl acetate is that waste water is entered by recovery tower top, and upper temp is controlled at 70 DEG C, obtains ethyl acetate,Waste water is discharged;The recovery of described n-hexane is that waste water is entered by recovery tower top, and upper temp is controlled at 69 DEG C, when recovery tower bottom risesTemperature, to 90 DEG C, stops heating, obtains n-hexane, and waste water is discharged.
- 3. the processing method of waste water in a kind of intermediate 4AA production according to claim 1, is characterized in that C step instituteThe flocculant of stating is the mixed liquor that bodied ferric sulfate, aluminium polychloride one of them or both mix with any proportioning.
- 4. the processing method of waste water in a kind of intermediate 4AA production according to claim 1, is characterized in that C step instituteThe combination that the hydrogenating reduction modification catalyst used of stating is Fe/C/Cu, its mass ratio is Fe:Cu:C＝70-80:10:1。
- 5. the processing method of waste water in a kind of intermediate 4AA production according to claim 1, is characterized in that C stepDescribed pH adjusting agent is inorganic acid.
- 6. the processing method of waste water in a kind of intermediate 4AA production according to claim 5, described in it is characterized in thatPH adjusting agent is the mixed liquor that sulfuric acid, hydrochloric acid one of them or both mix with any proportioning.
- 7. the processing method of waste water in a kind of intermediate 4AA production according to claim 1, is characterized in that f stepDescribed oxidant is hydrogen peroxide, clorox, perferrite, ferrate one of them or two or moreThe mixed liquor mixing with any proportioning.
- 8. the processing method of waste water in a kind of intermediate 4AA production according to claim 7, is characterized in that described oxygenAgent is 30% hydrogenperoxide steam generator, and its addition is 1-3ml/L; Described ferrous salt is ferrous sulfate, frerrous chlorideThe mixed liquor that one of them or both mix with any proportioning, its addition is 0.5-1.5g/L.
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| CN108083553A (en) * | 2017-11-27 | 2018-05-29 | 兰州大学白银产业技术研究院 | A kind of method for handling organic chemical waste water |
| CN113429059A (en) * | 2020-03-23 | 2021-09-24 | 南京理工大学 | Internal electrolysis-alkaline hydrolysis-biological integrated treatment process for hexanitrohexaazaisowurtzitane production wastewater |
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